Substituted derivatives of 1,1-dichloroalkene-1 and their preparation and uses

ABSTRACT

New substituted derivatives of 1,1-dichloroalkene-1 of the general formula: 
     
         R--X--(CH.sub.2).sub.n --CH═CCl.sub.2 
    
     in which R is one of an alkyl group and particularly an alkyl group of 1 to 12 carbon atoms, a phenyl group, chloro-phenyl group, dichloro-phenyl group, methyl-phenyl group, nitro-phenyl group, benzyl group, chloro-benzyl group, dichloro-benzyl group, methyl-benzyl group, phenetyl group and benzothiazolyl group; X is one of a sulfur atom a sulfinyl group and sulfonyl group; and n is an integer of 3,5 and 7.

The present invention relates to new and useful substituted derivativesof 1,1-dichloroalkene-1 and their preparation and uses. The presentinvention further includes a method of controlling bacterial and fungaldiseases of plants as well as a pesticidal and fungicidal compositioncontaining the new derivatives of 1,1-dichloroalkene-1 as the activeingredient.

Among the bacterial and fungal diseases of rice plant, rice blast(Piricularia oryzae) gives the most severe damage to rice plant. Inorder to control the rice blast, various organic mercuric compounds suchas phenyl mercuric acetate was widely been used in the rice field. Whenthe organic mercuric compounds have been applied as fungicide in therice field, it can be observed that a trade of mercuric compound remainsin the hull of rice grains which are harvested therefrom. For health ofpeople who like rice, it is now recommended to avoid the application oforganic mercuric pesticide and in stead thereof to employ any pesticidalcompound containing no mercury for the control of rice blast when riceplant has came into ears.

Some organic phosphorus compounds and some polychlorinated phenylcompounds have been used to practice as the fungicide for the control ofrice blast. Although certain compounds of them may have both theprotection effect and the curative effect on the rice plants in thetreatment of rice blast when tested in the laboratory, they can exhibitonly either one of the protection effect and the curative effect whentested in the field. Among the known pesticidal compounds, there is nopractical compound which is able to exhibit both the protection effectand the curative effect in combination for the treatment of rice blastwhen used in the rice field. In these circumstances, a demand isextensive and great to seek for such a mercury-free fungicide which ispractically able to exhibit the protection effect and the curative ortherapeutic effect in combination for the control of rice blast whenused in the rice field.

We have now found that the new substituted derivatives of1,1-dichloroalkene-1 of the general formula as stated below haveantimicrobial activity and exhibit excellent combined protective andcurative effects for the control of rice blast even when applied to inthe rice field.

We have further found that, among the new substituted derivatives, thesubstituted phenylthio-1,1-dichloroalkene-1 is superior in protectivefungicidal effect as well as in therapeutic effect to the unsubstitutedphenylthio-1,1-dichloroalkene-1.

Moreover, some substituted derivative of 1,1-dichloroalkene-1 of thegeneral formula as stated below can also be used as a fungicide forcontrolling sheath blight (Pellicularia sasaki), Bacterial leaf blight(Xanthomonas oryzae), Powdery mildew (Sphaerotheca fuliginea) andAnthracnose (Colletotrichum lagenarium).

Accordingly, the present invention provides new substituted derivativesof 1,1-dichloroalkene-1 of the general formula:

    R--X--(CH.sub.2).sub.n --CH═CCl.sub.2

in which R is an alkyl group, preferably an alkyl group of 1 to 12carbon atoms, a phenyl group, chlorophenyl group, dichloro-phenyl group,methyl-phenyl group, nitro-phenyl group, benzyl group, chloro-benzylgroup, dichloro-benzyl group, methyl-benzyl group, phenetyl group orbenzothiazolyl group; X is a further atom, sulfinyl group or sulfonylgroup; and n is an integer of 3,5 or 7.

The new derivatives of 1,1-dichloroalkene-1 of the present inventioninclude the following specific compounds as identified in Table 1 below.

                                      Table 1                                     __________________________________________________________________________                           Compound                                               Compounds              No.   Remarks                                          __________________________________________________________________________    5-Methylthio-1,1-      1     Clear, colorless                                 dichloropentene-1            liquid of B.P. of -  102- 108°                                         C./0.15 mmHg,                                                                 Refractive index                                                              (n.sub.D.sup.20)=1.5148                          7-Methylthio-1,1-      2     Clear, colorless                                 dichloroheptene-1            liquid of b.p. of                                                             136- 145° C. at 22 mmHg,                                               (n.sub.D.sup.20)=1.5070                          5-Isopropylthio-1,1-   3     Clear, yellow colored                            dichloropentene-1            liquid of b.p. of                                                             75- 82° C./0.15 mmHg,                                                  (n.sub.D.sup.20)=1.5020                          9-Isopropylthio-1,1-   4     Clear, yellow colored                            dichlorononene-1             liquid of b.p. of                                                             115- 123° C./0.3 mmHg,                                                 (n.sub.D.sup.20)=1.4938                          7-Butylthio-1,1-       5     Liquid of b.p. of                                dichloroheptene-1            103- 109° C. at 0.1 mmHg,                                              (n.sub.D.sup.20)=1.4979                          7-Dodecylthio-1,1-     6     Liquid of b.p. of                                dichloroheptene-1            172- 179° C. at 0.01 mmHg,                                             (n.sub.D.sup.20)=1.4880                          5-Phenylthio-1,1-      7     Liquid of b.p. of                                dichloropentene-1            114- 120° C. at 0.2 mmHg,                                              (n.sub.D.sup.20)= 1.5779                         7-Phenylthio-1,1-      8     Liquid of b.p.                                   dichloroheptene-1            of 124- 130° C. at                                                     0.01 mmHg,                                                                    (n.sub.D.sup.20)=1.5620                          5-(Para-chlorophenyl-  9     Liquid of b.p. of                                thio)-1,1-dichloro-          125- 132° C. at                           pentene-1                    0.006 mmHg,                                                                   (n.sub.D.sup.26.5)=1.5840                        7-(Para-chloro-        10    Clear, yellow colored                            phenylthio)-                 liquid of b.p. of                                1,1-dichloro-                135° C. to 140° C. at              heptene-1                    0.008 mmHg,                                                                   (n.sub.D.sup.22)=1.5781                          9-(Para-chloro-        11    Clear, brown colored                             phenylthio)-1,1-             liquid of b.p. of                                dichlorononene-1             more than 160° C./0.01 mmHg,                                           (n.sub.D.sup.20)=1.5185                          7-(2',5'-dichloro-     12    Liquid of b.p. of                                phenylthio)-1,1-             163° C. at 0.008 mmHg,                    dichloroheptene-1            (n.sub.D.sup.20)=1.5860                          5-(Para-methyl-        13    Clear, yellow colored                            phenylthio)-1,1-             liquid of b.p. of                                dichloropentene-1            118- 121° C./0.005 mmHg,                                               (n.sub.D.sup.20)=1.5718                          7-(Para-methyl-        14    Clear, yellow colored                            phenylthio)-1,1-             liquid of b.p. of                                dichloroheptene-1            137- 143° C. at 0.01 mmHg,                                             (n.sub.D.sup.20)=1.5587                          9-(Para-methyl-        15    Clear, yellow colored                            phenylthio)-1,1-             liquid of b.p. of                                dichlorononene-1             more than 100° C. at                                                   0.01 mmHg,                                                                    (n.sub.D.sup.20)=1.5486                          5-(Para-nitro-         16    Liquid of b.p. of                                phenylthio)-1,1-             more than 150° C. at                      dichloropentene-1            0.007 mmHg,                                      7-(Para-nitrophenyl-   17    Liquid of b.p. of                                thio)-1,1-dichloro-          more than 150° C. at                      heptene-1                    0.01 mmHg                                        5-Benzylthio-1,1-      18    Clear, yellow colored                            dichloropentene-1            liquid of b.p. of                                                             115- 125° C./0.01 mmHg,                                                (n.sub.D.sup.20)=1.5652                          7-Benzylthio-1,1-      19    Liquid of b.p. of                                dichloroheptene-1            145- 147° C./0.03 mmHg,                                                (n.sub.D.sup.29)=1.5529                          9-Benzylthio-1,1-      20    Clear, faint yellow                              dichlorononene-1             colored liquid of b.p.                                                        of 143- 147° C. at 0.003                                               mmHg,                                                                         (n.sub.D.sup.20)=1.5437                          5-(Para-chloro-        21    Liquid of b.p. of                                benzylthio)-1,1-             141- 144° C. at                           dichloropentene-1            0.015 mmHg                                                                    (n.sub.D.sup.20)=1.5749                          7-(Para-chlorobenzyl-  22    Liquid of b.p. of                                thio)-1,1-dichloro-          150- 160° C./0.007 mmHg,                  heptene-1                    (n.sub.D.sup.20)=1.5629                          7-(2',4'-dichloro-     23    Liquid of b.p. of                                benzylthio)-1,1-             170- 175°  C./0.01 mmHg,                  dichloroheptene-1            (n.sub.D.sup.20)=1.5638                          5-(Para-methyl-        24    Liquid of b.p. of                                benzylthio)-1,1-             118- 121° C. at                           dichloropentene-1            0.005 mmHg,                                                                   (n.sub.D.sup.20)=1.5718                          7-(Para-methyl-        25    Liquid of b.p. of                                benzylthio)-1,1-             137- 143° C. at 0.01 mmHg,                dichloroheptene-1            (n.sub.D.sup.20)=1.5587                          5-Phenetylthio-        26    Liquid of b.p. of                                1,1-dichloropentene-1        127- 130° C. at 0.003 mmHg,                                            (n.sub.D.sup.20)=1.5596                           ##STR1##                                                                     7-Phenetylthio-1,1-    27    Liquid of b.p. of                                dichloroheptene-1            142- 150° C. at 0.005 mmHg,                                            (n.sub.D.sup.20)=1.5552                          5-[benzothiazolyl-     28    Clear, brown colored                             (2)-thio]-1,1-               liquid of b.p. of                                dichloropentene-1            160° C./0.02 mmHg,                                                     (n.sub.D.sup.36.5)=1.6387                         ##STR2##                                                                     7-[Benzothiazolyl-     29    Red colored liquid of                            (2)-thio]-1,1-               b.p. of more than 140° C.                 dichloroheptene-1            at 0.1 mmHg,                                                                  (n.sub.D.sup.20)=1.6102                          9-[Benzothiazolyl-     30    Clear, brown colored                             (2)-thio]-1,1-               liquid of b.p. of                                dichlorononene-1             more than 145° C. at                                                   0.01 mmHg,                                                                    (n.sub.D.sup.20)=1.5579                          7-Methylsulfinyl-      31    Clear, colorless                                 1,1-dichloroheptene-1        liquid of b.p. of 133-                                                        138° C. at 0.2 mmHg,                                                   (n.sub.D.sup.20)=1.5167                          7-(Para-chloro-        32    Liquid of b.p. of more                           benzylsulfinyl)-             than 180° C. at 0.01 mmHg,                1,1-dichloroheptene-1        (n.sub.D.sup.20)=1.5752                          7-Phenylsulfonyl-1,1-        Liquid of b.p. of                                dichloroheptene-1      33    150- 160° C./0.02 mmHg,                                                (n.sub.D.sup.24)=1.5393                          7-(Para-chlorophenyl-        Clear, yellow colored                            sulfonyl)-1,1-         34    liquid of b.p. of                                dichloroheptene-1            180- 190° C. at 0.01                                                   to 0.02 mmHg,                                                                 (n.sub.D.sup.29)=1.5508                          7-(2',5'-dichloro-     35    Liquid of b.p. of more                           phenyl-sulfonyl)-            than 150° C. at 0.08 mmHg,                1,1-dichloropeptene-1        (n.sub.D.sup.20)=1.5790                          __________________________________________________________________________

the new substituted derivatives of 1,1-dichloroalkene-1 of the presentinvention may be prepared in various ways.

A most convenient way to prepare them is to react a mercaptide of theformula R-SM with a trichloroalkene-1 of the formula Cl--(CH₂)_(n)--CH═CCl₂ in a suitable organic solvent such as ethanol in which thereagents are soluble. The reaction proceeds according to the followingequation:

    R--SM + Cl--(CH.sub.2).sub.n --CH═CCl.sub.2 → R--S--(CH.sub.2).sub.n --CH═CCl.sub.2 + MCl

wherein R and n have the same meanings as defined hereinbefore; and M isan alkali metal atom or ammonium group. In this reaction, as thestarting mercaptide, there may be used those which correspond to thefollowing mercaptans:- methyl mercaptan, ethyl mercaptan, isopropylmercaptan, butyl, mercaptan, dodecyl mercaptan, phenyl mercaptan,2-chlorophenyl mercaptan, 4-chlorophenyl mercaptan, 4-nitrophenylmercaptan, 2,4-dichlorophenyl mercaptan, 2,5-dichlorophenyl mercaptan,3,4-dichlorophenyl mercaptan, 4-methylphenyl mercaptan, benzylmercaptan, 4-chlorobenzyl mercaptan, 4-methylbenzyl mercaptan, phenetylmercaptan, benzothiazolyl mercaptan and the like. The mercaptide may beformed in situ in the reaction medium by reacting the correspondingmercaptans with an alkali metal. The starting material Cl--(CH₂)_(n)--CH═CCl₂ may be prepared by telomerization of ethylenically unsaturatedaliphatic hydrocarbons such as ethylene with carbon tetrachloride,followed by the dehydrochlorination.

A further way to prepare the new derivatives of 1,1-dichloroalkene-1 ofthe present invention is to oxidise the products of the above-mentionedreaction with hydrogen peroxide or organic per-acid such as perbenzoicacid or peracetic acid. In this case, the reaction may be represented bythe following equation: ##STR3## wherein R and n have the same meaningsas defined above, and m is an integer of 1 or 2.

According to the present invention, therefore, there is provided aprocess for the preparation of the new substituted derivatives of1,1-dichloroalkene-1 of the general formula:

    R--X--(CH.sub.2).sub.n --CH═CCl.sub.2

in which R is an alkyl group, a phenyl group, chlorophenyl group,dichlorphenyl group, methylphenyl group, nitrophenyl group, benzylgroup, methylbenzyl group, chlorobenzyl group, dichlorobenzyl group,phenetyl group or benzothiazolyl group; and X is a sulfur atom or asulfinyl group or sulfonyl group; and n is an integer of 3,5 or 7,characterized in that a mercaptide of the formula:

    R--SM

in which R has the same meanings as state above and M is an alkali metalatom or ammonium group is reacted with a trichloroalkene-1 of theformula:

    Cl--(CH.sub.2).sub.n --CH═CCl.sub.2

in which n is 3,5 or 7, in the presence of an organic solvent in whichthe reagents are soluble, and that the substituted 1,1-dichloroalkene-1derivatives so obtained is oxidised, if desired.

As mentioned previously, the new substituted derivatives of1,1-dichloroalkene-1 of the present invention have antimicrobialactivity, and particularly fungicidal activity to Piricularia oryzae,and they are useful for the protection of plants from attack byphyto-pathogenic micro-organisms as well as for the therapeutictreatment of plants which have been infected by phyto-pathogenicmicro-organisms.

According to the present invention, therefore, there is also provided amethod of controlling fungal diseases of plants which comprises applyingto plants an effective amount of at least one of the new substitutedderivatives of 1,1-dichloroalkene-1 of the general formula as statedhereinbefore.

In particular, the present invention provides a method of controllingthe rice blast which comprises applying to rice plant an effectiveamount of at least one of the new substituted derivatives of1,1-dichloroalkene-1 of the general formula as stated hereinbefore.

For use in the control of fungal diseases, the new substitutedderivatives of 1,1-dichloroalkene-1 of the present invention may beapplied to plants, in admixture with an inert carrier which may beeither solid or liquid.

Accordingly, the present invention further provides a fungicidalcomposition which contains as the active ingredient at least one of thenew substituted derivatives of 1,1-dichloroalkene-1 of the generalformula as stated hereinbefore, in admixture with a carrier which isinert to the active ingredient compound.

The fungicidal composition of the present invention may be formulated inthe form of dust, wettable powder, solution, suspension or emulsion, asdesired. Solid carrier may be, for example, diatomaceous earth, talc,kaolin, clay, and the like. Liquid carrier may be, for example, waterand organic solvents such as xylene, toluene, benzene, methanol,ethanol, acetone, cyclohexanone, dimethylformamide and the like. Thefungicidal composition of the present invention further may contain avariety of surface-active agents as emulsifying agent, spreading agent,dispersing agent and/or wetting agent etc.

The proportion of the active ingredient in the composition of thepresent invention may vary in a wide range but preferably in a range of1% to 50% by weight. The composition of the present invention may bedispersed or diluted in water for spraying.

When the composition of the present invention is prepared in the form ofan emulsifiable solution, it may be recommended that one or moreemulsifying agents such as polyoxyethylene alkylaryl ethers,polyoxyethylene alkyl ethers, polyoxyethylene aliphatic acid esters,alkylaryl sulfonates and polyoxyethylene polyalkyldiphenyl ethers or amixture of two or more of them is or are incorporated at an amount of 5to 15% by weight into a solution of the active ingredient compounddissolved in an organic solvent such as xylene, toluene, or mixedorganic solvents.

When the composition of the present invention is formulated as wettablepowder, it is then recommendable that 1 to 3% by weight of a wettingagent such as alkylaryl sulfonates, polyoxyethylene alkylaryl etherlauryl sulfate and polyoxyethylene alkylaryl sulfonates, as well as 1 to3% by weight of a dispersing agent such as lignin sulfonate, polyvinylalcohol, carboxymethyl cellulose, methyl cellulose, alkylarylsulfonate-formaldehyde condensate are incorporated in a powdered mixtureof the active ingredient compound with a suitable solid carrier such astalc.

If desired, the composition of the present invention may further containvarying amounts of another pesticide, fungicide such as ferricmethane-arsonate, pesticide such as sevin (registered trade name),Sumithione (registered trade name) and BHC etc.

The invention is now illustrated with reference to the followingExamples, but to which the present invention is not limited.

EXAMPLE 1

To a solution of 23 g. (0.1 mol) of metallic sodium in 150 ml. of ethylalcohol was added 14.4 g. (0.1 mol) of benzyl mercaptan, and the mixturewas heated for 1 hour under agitation. To the mixture was then added 23g. (0.1 mol) of 1,1,9-trichlorononene-1, and the admixture was agitatedat about 80° C. for 8 hours. After the completed reaction, the reactionmixture was poured into a large quantity of water. An oil deposited,which was then extracted with benzene. The extract was dried withanhydrous sodium sulfate and distilled to evaporate the benzene. Theconcentrated residue was purified by fractional distillation undervacuum. 25.0 g. of 9-benzylthio-1, 1-dichlorononene-1 of the formula:

    C.sub.6 H.sub.5 --CH.sub.2 --S--(CH.sub.2).sub.7 --CH═CCl.sub.2

was obtained as a clear, faint yellow colored liquid having boilingpoint of 143°-147° C. at 0.003 mmHg. Yield: 79% on the basis of thetheoretical value.

EXAMPLE 2

The procedure of Example 1 was repeated using methyl mercaptan and1,1,5-trichloropentent-1. 5-Methylthio- 1,1-dichloropentene-1 of theformula CH₃ --S--(CH₂)₃ CH═CCl₂ was obtained as a clear and colorlessliquid which boiled at 102°-103° C. at 0.15 mmHg.

EXAMPLE 3

The procedure of Example 1 was repeated using isopropyl mercaptan and1,1,5-trichloropentene-1. 5-Isopropylthio-1,1-dichloropentene-1 of theformula ##STR4## was obtained as clear and yellow colored liquid whichboiled at 75°-82° C. at 0.15 mmHg.

EXAMPLE 4

To a solution of 2.3 g. of sodium in 150 ml. of ethanol was added 124 g.(0.1 mol) of para-methylphenyl mercaptan, and the mixture was heated for30 minutes under agitation. 20.2 g. (0.1 mol) of1,1,7-trichloroheptene-1 was then added thereto, and the mixture wasagitated at about 80° C. for 8 hours. After the completed reaction, thereaction mixture was poured into water. The oily material deposited wasextracted with benzene. The organic layer was dried with anhydroussodium sulfate and concentrated by evaporating the benzene. When theresidue was distilled under vacuum,7-(para-methylphenylthio)-1,1-dichloroheptene-1 of the formula ##STR5##was obtained as a clear and yellow colored liquid which boiled at137°-143° C. at 0.01 mmHg. Yield was 25.6 g. (88.5%).

EXAMPLE 5

The procedure of Example 4 was repeated using 0.1 mol. of benzothiazolylmercaptan and 0.1 mol. of 1,1,7-trichloroheptene-1. At a yield of 81%,7-[benzothiazolyl-(2)-thio]-1,1-dichloroheptene-1 was obtained as redcolored liquid which boiled above 140° C. at 0.1 mmHg.

EXAMPLE 6

Fifty g. of an aqueous solution containing 20% of sodiummethylmercaptide was dissolved in 150 ml. of dimethylformamide, and 28.8g. of 1,1,7-trichloroheptene-1 was added thereto at room temperaturetogether with a catalytic amount of potassium iodide. The mixture washeated at 80°-90° C. for 10 hours under agitation. After the completedreaction, the reaction mixture was cooled to room temperature and thenpoured into about 1.5 l. of water. The oily material deposited wasextracted with benzene. The organic layer was dried with anhydroussodium sulfate and concentrated by evaporating the solvent. When theresidue was distilled under vacuum, 28 g. of7-methylthio-1,1-dichloroheptene-1 was obtained as clear and colorlessliquid which boiled at 136°-145° C. at 22 mmHg.

EXAMPLE 7

Twenty g. of an aqueous solution of 30% hydrogen peroxide was added to asolution of 21.3 g. of 7-methylthio-1,1-dichloroheptene-1 in 150 ml. ofglacial acetic acid under agitation while the reaction temperature waskept at about 15° C. by cooling the reaction mixture with ice-water. Themixture was further stirred for 1 hour at 15° C. After the completedreaction, the reaction mixture was poured into about 2 l. of water andthe oily material deposited was extracted with benzene.

The organic layer was dried with anhydrous sodium sulfate and thenconcentrated by evaporating the solvent. When the residue was distilledunder vacuum, 17.2 g. of 7-methylsulfinyl-1,1-dichloroheptene-1 wasobtained as clear and colorless liquid which boiled at 133°-138° C. at0.2 mmHg.

EXAMPLE 8

To a solution of 28.9 g. (0.2 mol) of parachlorophenyl mercaptan in 50ml. of benzene was added dropwise 11.5 g. of a sodium dispersioncontaining 40% metallic sodium which corresponded to 0.2 mol of sodium.After the addition was complete, the mixture was heated for 2 hoursunder reflux. 100 ml. of dimethylformamide and 40.3 g. (0.2 mol) of1,1,7-trichloroheptene-1 were added thereto, and the mixture was furtherheated for 15 hours under reflux. After the completed reaction, thereaction mixture was washed with water. The remaining benzene solutionwas then dried with anhydrous sodium sulfate and concentrated bydistilling off the solvent. When the residue was distilled under vacuum,35 g. of 7-(para-chlorophenylthio)-1,1-dichloroheptene-1 was collectedas a fraction which boiled at 135°-140° C. at 0.008 mmHg. This productwas a clear and yellow colored liquid.

EXAMPLE 9

To a solution of 20 g. of para-chlorobenzene sulfinic acid sodium saltin 200 ml. of dimethylformamide was added dropwise 20 g. of1,1,7-trichloroheptene-1 under agitation. When the addition had beencompleted, the mixture was heated at 80 to 90° C. for 10 hours. Afterthe completed reaction, the reaction mixture was poured into 1 l. ofwater. The organic layer separated was extracted with benzene and theextract was dried with anhydrous sodium sulfate. When the residue wasdistilled under vacuum, 16 g. of7-(para-chlorophenylsulfonyl)-1,1-dichloroheptene-1 was collected as afraction which boiled at 180°-190° C. at 0.01 -0.02 mmHg. This productwas a clear and yellow colored liquid. Infra-red absorption spectrum ofthis product showed the absorption band at 1150 cm⁻¹ due to the presenceof the sulfonyl group.

EXAMPLE 10

Five Parts (by weight) of the compound No. 1, that is,5-methyl-1,1-dichloropentene-1, 45 parts of talc, 47 parts of clay and 3parts of white carbon were mixed together and ground in a mill. Thepowder may be applied to plants in the form of dust.

EXAMPLE 11

Five Parts (by weight) of the compound No. 16, this is,5-(para-nitro-phenylthio)-1,1-dichloropentene-1, 45 parts of talc, 47parts of clay and 3 parts of white carbon were mixed together and groundin a mill. The resulting powder may be suitable for dusting.

EXAMPLE 12

Twenty five Parts (by weight) of the compound No. 15, that is,9-(para-methyl-phenylthio)-1,1-dichlorononene-1, 30 parts ofdiatomaceous earth, 10 parts of white carbon, 30 parts of clay and 5parts of a wetting agent (a mixture of polyalkylaryl polyglycol ethers)were mixed together and ground. The wettable powder so obtained mayeasily be diluted in water and the resulting suspension may be suitablefor spraying.

EXAMPLE 13

Twenty five Parts of the compound No. 16, that is,5-(para-nitrophenylthio)-1,1-dichloropentene-1, 30 parts of diatomaceousearth, 10 parts of white carbon, 30 parts of clay, and 5 parts of awetting agent (a mixture of alkylaryl polyglycol ethers) were mixedtogether and ground. The wettable powder so obtained may readily dilutedwith water and the resulting suspension may be suitable for spraying.

EXAMPLE 14

Fifty Parts of the compound No. 13, that is,5-(Para-methylphenylthio)-1,1-dichloropentene-1, 35 parts of xylene and15 parts of an emulsifying agent (a mixture of alkylaryl polyglycolethers and alkylaryl sulfonates) were mixed together and agitated toprepare a uniform solution. This emulsifiable solution may readily beconverted into an emulsion suitable for spraying, when diluted withwater.

EXAMPLE 15

Fifty Parts of the compound No. 18, that is,5-benzylthio-1,1-dichloropentene-1, 35 parts of xylene and 15 parts ofan emulsifying agent (a mixture of alkylaryl polyglycol ethers andalkylaryl sulfonates) were mixed together and agitated enough to give auniform solution. The resulting emulsifiable solution may readily beconverted into an emulsion suitable for spraying, when diluted withwater.

EXAMPLE 16

This Example illustrates the tests of controlling rice blast bytreatment with the new substituted derivatives of 1,1-dichloroalkene-1of this invention.

The therapeutic effect test and the protective effect test were madewith respect to 4-leaf stage paddy field rice plant (Variety, AichiAsahi) planted in a pot of 15 cm diameter, respectively.

An emulsifiable concentrate as prepared according to Example 4, whichcontains an active compound as shown in the following Table 2, wasdiluted with water to a concentration of 500 ppm of the active compoundand the thus diluted solution was sprayed in an amount of 30 cc per pot.

In the therapeutic effect test, the rice plants grown in pots wereinoculated with aqueous suspension of spores of Piricularia oryzae andthe diluted solution of chemicals was sprayed on infested plants on the3rd day after inoculation. The effectiveness was assessed on the 7th dayafter inoculation.

On the other hand, in the protective effect test, the diluted solutionwas prayed on the 3rd day before the inoculation. The effectiveness wasassessed on the 7th day after inoculation.

The controlling value was calculated according to the followingequation.

Controlling value (%) = ##EQU1## In the therapeutic effect test, theterm "disease degree" in the above equation means a ratio of the numberof actively diseased spots to the total number of actively andinactively diseased spots. In the protective effect test, the diseasedegree merely means the number of diseased spots.

                  Table 2                                                         ______________________________________                                        Experiment result (therapeutic effect)                                        ______________________________________                                        Active compound                                                                           Concentration Controlling                                         tested      (ppm.)        value                                               ______________________________________                                        Compound 7  500           56                                                  10          "             95                                                  11          "             78                                                  13          "             75                                                  14          "             100                                                 15          "             79                                                  16          "             71                                                  17          "             73                                                  18          "             90                                                  19          "             99                                                  20          "             98                                                  21          "             97                                                  22          "             100                                                 23          "             91                                                  24          "             74                                                  25          "             92                                                  26          "             75                                                  27          "             99                                                  31          "             97                                                  32          "             71                                                  33          "             73                                                  34          "             72                                                  35          "             71                                                  ______________________________________                                    

What we claim is:
 1. 7-(Para-chlorophenylthio)-1,1-dichloroheptene-1. 2.7-Benzylthio-1,1-dichloroheptene-1. 3.7-(Para-methylphenylthio)-1,1-dichloroheptene-1. 4.5-(Para-chlorophenylthio)-1,1-dichloropentene-1. 5.5-(Para-methylphenylthio)-1,1-dichloropentene-1. 6.9-(Para-chlorophenylthio)-1,1-dichlorononene-1.